Mothproofing of keratinaceous materials



United States Patent "ice MOTHPROOFING 0F KERATINACEO'US MATERIALS Lloyd M. Kozlolf, Chicago, Ill., assignor, by direct and mesue assignments, of seventy percent to Hightower- Morse & Company, Chicago, 111., a corporation of Delaware, ten percent to Bernard Wolnak, Highland Park, and five percent to Joseph P. Antonow, Chicago, Ill.

No Drawing. Filed Dec. 17, 1957, Ser. No. 703,265 12 Claims. c1.s 17

This invention relates to the production of moth resistant products and more particularly relates to the production of moth resistance keratinaceous materials and to methods of producing the same.

It is well known in the art that woolen goods and insect in which form it may subsist substantially upon a V diet of keratinaceous protein. Many methods have been proposed for reducing the damage caused by the larva of the webbing clothes moth, which include storage in tightly closed containers such as cedar chests, or the use of solid Volatile moth repellent materials such as naphthalene or paradichlorobenzene, which are usually stored with the garments to be protected.

It has also been proposed and demonstrated that the use of various insecticidal materials such as DDT or related chlorinated insecticides results in a substantial reduction in damage to clothing and other materials which are stored or unused for a substantial period of time.

While the foregoing methods have been used to advantage under varying circumstances, they have certain drawbacks which render their use undesirable in many respects. For example, the use of naphthalene or paradichlorobenzene as a moth repellent usually results in the saturation of the fibers by the vapors of the repellent so that clothing retaining the characten'stic odor thereof is not ready for immediate use after storage for a prolonged period in confined or intimate contact with these materials without a rather substantial airing out. Furthermore, repellents are not suitable for the protection of Woolen carpeting, draperies or the like, which are often subject to mothdamage, since their effectiveness is largely dependent upon confinement of their vapors in relatively small spaces. v

With regard to chlorinated insecticides such as DDT, it is well understood that these materials are toxic organic compounds which may be cutaneously absorbed by persons coming into contact therewith for prolonged periods, and they have been criticized for this reason. Other chlorinated insecticides may have staining or other characteristics which render their use inexpedient. Furthermore these materials (DDT and the like) are relatively soluble in organic solvents and are therefore readily removed in a single cleaning, and retreatment is required.

Accordingly, one object of the present invention is the production of keratinaceous materials which are resistant to moth damage over a prolonged period of time.

Another object of the present invention is the provision of a process for mothproofing wool and other keratina ceous materials which is not detrimental to the physical properties of the goods.

Another object is the provision of a moth resistant Patented July 19, 1960 keratinaceous material which is relatively free of toxic ingredients.

Another object is the provision of a method for rendering a keratinaceous material moth resistant, which does not affect the color or appearance of the goods to which it is applied. 7

A still further object is the production of a moth resistant fibrous --woolen material whose properties are relatively unalfected by heat.

A still-further object is the provisionof moth resistant woolen goods which are relatively unaffected by and resistant to dry cleaning and washing.

A still further object is the provision of a process for rendering woolen goods resistant to moth damage which is readily integrated in the wool production process.

These and other objects of the present invention will be seen from the following specification and appended claims.

In one embodiment the present invention comprises a keratinaceous material impregnated with a relatively small amount of pyridine-3-sulfonic acid. It is also contemplated asa part of this invention to provide a method of treating Woolen or other keratinaceous material with benzimidazole to'produce a moth resistant product.

With reference to the materials to which the broad conceptof the present invention is'applicable, it should be stated that they in large part may be termed keratinaceous substances, as described above, which are so characterized since their structure is largely based upon the protein keratin. Materialsof this generaldescription include woolens, furs, hair products of all sorts, feathers, and the like. Of course, it is to be understood that damage by cothes moth larvae is not necessarily restricted to materials made wholly from these substances, but also may occur in fabrics containing these materials in conjunction with other fibers which are naturally moth resistant. Particularly it should be understood that this invention is applicable to woolen blends with materials 'similar material is as described above, pyridine-3-sulfonic acid. It has been found that by impregnating woolen products and similar goods with a relatively small amount of pyridine-3-sulfonic acid, sustained protection against the hatching of clothes moth eggs and concomitant larva damage may be obtained.

' Generally the minimum concentration of pyridine-3- sulr'onic acid that should be present on the woolen fibers is on the order of at least 0.5 weight percent. It has been found that woolens treated with pyridine-3 sulfonic acid at the above or higher concentrations have prolonged resistance to moth damage. While these con centrations have been found to be eifective, concentrations of as high as 7.5 weight percent may be utilized to more adequately protect the goods thereby impregnated. A mostpreferred range of concentration which gives substantially complete protection is from 1 to 5 Weightpercent. Alternatively, the concentration ofnnpregnant may be expressed in terms of weight per unit area. Thus the range of pyridine-3-sulfonic acid broadly includes from about 0.15 to about 2.5 milligrams per square centimeter, and a most preferred range from 0.3 to about 1.6 milligrams per square centimeter.

While it is possible to use higher concentrations of pyridine-3-sulfonic acid, it should be stated that no particular advantage is achieved thereby and the use of excessive amounts thereof is merely economically inexpedient.

The method of treating the keratinaceous material comprises impregnation of the keratinaceous substance or fabric with pyridine-3-sulfonic acid in aqueous solution. This impregnation may be carried out in an aqueous medium for a period of time suflicient to insure the impregnation or adsorption of a sufiicient concentration of pyridiue-3-sulfonic acid upon the surfaces of fibers in the Woolens or other keratinaceousmaterials making up the goods treated. For example, it has been found that aqueous solutions of pyridine-3-sulfonic acid'containing the latter in a concentration of 1 to 20 milligrams per milliliter are suitable impregnating solutions for woolen fabrics. The time of residence or treatment in such solution may vary, it being understood that the degree of adsorption varies with the length of treatment, thus periods of time from fifteen minutes to as long as three hours or more may be utilized.

The process is preferably carried out at elevated temperatures substantially above normal room temperature, since the concentration of pyridine-3-sulfonic acid attainable in aqueous solutions decreases at lower temperatures. Broadly the most preferred temperatures are between 50 and 100 C. More elevated temperatures may also be utilized. Of course, with temperatures lower than 50 C. the rate of impregnation is decreased and longer times of impregation are required to insure depositing the requisite amount of impregnant.

While the process of the present invention may be carried out successfully in substantially neutral or alkaline aqueous solutions, it has been found that the adsorption to the fibers of the goods so treated is enhanced by carrying out the treatment under acid conditions ranging from a pH of about 1 to about 6. Mineral acids, such as sulfuric or hydrochloric acid, are useful to produce the desired acid conditions as well as acid salts such as, for example, Glaubers salt. This characteristic is particularly valuable in that the mothproofing treatment may bercarried out simultaneously and in conjunction with wool dyeing operations since many of these dyeing operations are carried out under acid conditions.

The process of the present invention and the resulting product may be more clearly understood by reference to the following example:

prised an aqueous solution of pyridine-3-sulfonic acid, the latter being present in concentrations ranging from 1 to 20 milligrams per milliliter of solution. Twenty milliliter batches were made of each of the various concentrations utilized. The pH of the impregnating bath was adjusted to between about 2 and 2.5 by the addition of Glaubers salt '(Na SO .10H- O) and aqueous sulfuric acid. Preparatory to the impregnation the wool swatches were first thoroughly wet in water maintained at about 40 C. The prewet swatches were then transferred to the impregnating bath and the temperature of the bath was brought to 65 C. The impregnation was continued for a one hour period after which time the sample swatches were removed from the bath, pressed free of excess fluid, and air dried. These swatches were then placed in glass vessels with from 10 to 12 adult clothes moths (Tineola biselliella). The moths remained in contact with the wool swatches a period of five days to permit egg laying after which time the moths were withdrawn and the individual swatches transferred to Petri dishes. The incubation of the samples was continued and the emerging larvae on each swatch counted. Damage to the cloth was visually determined after a fourteen day period. In the following table the term percent efiiciency relates to the degree of protection achieved by the impregnation and is derived from the ratio of the decrease in the weight of debris from moth larvae in an untreated control swatch. The following formula was adopted:

Percent efiicien cy g X 100 wherein The following table gives the results of the above experiments:

TABLE I.-EFFEOT 0F PYRIDINE-3-SULFONIC ACID APPLIED FROM SIMULATED ACID BA'IB'S 1 Wool treated at 65 C. for one hour.

EXPERIMENT Impregnation of wool with pyridine-.i-sulfonic acid Samples of dirt-free, undyed wool swatches, approximately 7.5 centimeters square and weighing about 1.5 grains, were impregnated with various concentrations of pyridine-B-sulfonic acid. The impregnating bath com- In an experiment similar to that described above, impregnations were carried out using pyridine-3-sulfonic acid at elevated temperatures (boiling). The results are indicated in Table II. It should be noted that the use of higher temperatures for the impregnation results in a relatively higher absorption of the impregnant into the wool fibers 'over an equivalent time period.

TABLE II.EFFEC'I OF PYRIDINE-Zi-SULFONIC ACID APPLIED FROM SIMULATED DYE BATHS Concentration Pyridine-3-Sulfonic Acid No. of Wt. of Absorbed by Wool Larvae Debris, Percent observable Enlarged mg. Efiicieney Damage Initial (mg/ml.)

(mgJcm Wt.

Percent 1 1.8 97 None. 11 12.4 82 None. 32 71.0 Considerable.

I Boiledtor one hour.

As illustrated in the foregoing tables, very slight or no damage was indicated in the treated samples.

While the foregoing impregnation of woolen swatches was carried out under acid conditions, excellent results have also been obtained by the impregnation of pyridine- 3-sulfonic acid from aqueous solutions under substantially neutral conditions. However, it should be noted that the utilization of acid conditions in the impregnating bath is beneficial in that it permits the impregnation of woolens or other materials concomitantly with dyeing of the goods, which is often carried out under acid conditions. Tests with various acid wool dyes applied to samples concomitantly with pyridine-3-sulfonic acid indicated no alteration in the efficiency of the treatment or in the degree of protection achieved.

Acid wool dyes 1 such as Chromolan Grey, Alizarine Sapphire SE (Color Index No. 63,000), Croceine Scarlet MOO #90 (Color Index No. 27,290), and Eric Scarlet B (Color Index No. 22,240), were successfully utilized in the foregoing manner, which acid bath impregnation carried out concomitantly with the dyeing operation is advantageous in a great many wool processing operations.

It is also true that pyridine-S-shlfonic acid may be impregnated in neutral or alkaline media concomitant with or Without the addition of alkaline dyes. For example, an

alkaline dye such as Superchrome B, impregnated from the same bath as pyridine-3-su1fonic acid, gave excellent results.

While the use of pyridine-3-sulfonic acid results in protection of woolen and similar keratinaceous materials from the damage by the common webbing clothes mot-h larvae, it should be noted that the chief activity is to diminish the normal expected emergence of larvae from eggs laid by the adult insect. It is also contemplated as a part of this invention to incorporate with pyridine-3-sulfonic acid a small amount of a larvicidal mothproofing agent such as benzimidazole. The utility of benzimidazole in this respect is described in our copending application, Serial No. 703,289, filed December 17, 1957. Impregnation with .both pyridine-3 -sulfonic acid and benzimidazole in the concentration range-s indicated in the foregoing gave excellent protection to the woolen fabrics wherein the same was incorporated.

The impregnation of woolen fabrics with pyridine-'3- sulfonic acid produces a moth resistant fabric which retains a surprising degree of efiiciency after dry cleaning or washing. This valuable property permits the impregnation of woolens or other materials which provides in a single impregnation a moth-resistant fabric which does not require retreatment over a prolonged period.

While the foregoing specific examples have indicated that the impregnation step may be carried out over a one-hour period, it is to be understood that the length of impregnation necessary to produce the products of the present invention may be from about fifteen minutes to about three hours, and by proper adjustment of the All dyes are products of National Aniline Corporation.

(All dyes are products of National Aniline Corporation.

pregnation of the wool from aqueous baths, it is possible to achieve the same purpose by impregnation from organic solvents, aqueous dispersions of organic materials such as emulsions, or by spraying the pyridine 3- sulfonic acid onto the wool. While pyridine-S-sulfonic acid has been used in the mothproofing of woolen materials, other keratinaceous protein based materials may be similarly treated. Furthermore, it is possible to utilize other mot-hpro-ofing materials in conjunction with pyridine-3-sulfonic acid to achieve a broad protection and provide mothproofing for a variety of materials.

While several particular embodiments of. this invention are shown above, it will be understood, of course, that the invention is not to be limited thereto, since many modifications may be made, and it is contemplated, therefore, by the appended claims, to cover any such modifications as fall within the true spirit and scope of this invention.

I claim:

1. A fibrous, moth resistant material comprising a keratinaceous based fibrous material impregnated with a small amount of pyridine-3-sulfonic acid.

2. A fibrous, moth resistant material comprising a keratinaceous protein containing fibrous material impregnated with a small amount of pyridine-S-sulfonic acid.

3. A moth resistant woolen treated with a relatively small amount of pyridine-3 -sulfonic acid.

4. A moth resistant woolen comprising a wool containing fabric treated with a relatively small amount of pyridine-3-sulfonic acid.

5. A moth resistant keratinaceous product comprising a keratinaceous fibrous material impregnated with at least 0.5 weight percent of pyridine-3-sulfonic acid.

6. A process for rendering a fibrous keratinaceous material moth resistant which comprises impregnating said keratinaceous material with pyridine-3-sulfonic acid.

7. The process of claim 6 wherein the impregnation is carried out in aqueous solution.

8. The process of claim 6 wherein the impregnation is carried out under acid conditions.

9. The process of claim 6 wherein the pyridine-B-snlfonic acid is impregnated in the keratinaceous fibers at a concentration of at least 0.5 weight percent.

10. The process of claim 6 wherein the impregnation is carried out in a nonaqueous solution.

11. The process of claim 6 wherein the impregnant is carried out by spraying the keratinaceous material with the pyridine-B-sulfonic acid.

12. A process of mothproofing and dyeing wool which comprises contacting wool with an aqueous solution containing acid wool dyes and pyridine-3-sulfonic acid under acid conditions to produce a dyed wool having pyridine -3- sulfonic acid impregnated therein.

References Cited in the file of this patent UNITED STATES PATENTS Creeley May 12, 1942 Higgins Sept. 27, 1949 OTHER REFERENCES King: Chemicals Evaluated as Insecticides, US. Dept. Agri., May 1954, p. 298. 

12. A PROCESS OF MOTHPROOFING AND DYEING WOOL WHICH COMPRISES CONTACTING WOOL WITH AN AQUEOUS SOLUTION CONTAINING ACID WOOL DYES AND PYRIDINE-3-SULFONIC ACID UNDER ACID CONDITIONS TO PRODUCE A DYED WOOL HAVING PYRIDINE-3SULFONIC ACID IMPREGNATED THEREIN. 